Trivalent Lanthanide Interactions with a Terdentate Bis(dialkyltriazinyl)pyridine Ligand Studied by Electrospray Ionization Mass Spectrometry

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Abstract
The 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridines (DATPs) belong to a new family of extracting agents recently developed in the framework of nuclear fuel reprocessing. These molecules exhibit exceptional properties to separate actinides(III) from lanthanides(III) in nitric acid solutions. A previous work showed that electrospray ionization mass spectrometry (ESI-MS) is a reliable technique to provide solution data such as stoichiometries and conditional stability constants of various DATP complexes with europium and evidenced the unusual capability of DiPTP [bis(di-iso-propyltriazinyl)pyridine] ligand to form 1:3 complexes in nitric acid solution. This latter result is further investigated by considering DiPTP complexation features with the complete lanthanide family. As a starting point of the experimental procedure used for stability constant evaluation, the intensity distribution of ions detected by ESI-MS is studied for solutions containing Ln(NO3)3 in water/methanol (1:1 v/v) with the pH value set at 2.8 and 4.6 by HNO3 additions. At pH 2.8, the nitrate anions are found to prevent lanthanides from processes occurring within the ion source: redox phenomena or gas-phase reactions with methanol which give species such as [Ln(MeO)2]+. Thus, the total intensity of MS signals from [Ln(NO3)2(H2O)p(MeOH)n]+ ions is found proportional to the metal ion concentration. At pH 4.6, with lower nitrate concentration, the nature of the species identified on mass spectra depends on the electronic properties of the lanthanide elements. It is shown that Ln(III) complexation with DiPTP leads to the exclusive formation of 1:3 complexes with the whole lanthanide series which may be due not only to the hydrophobic exterior of the ligand but also to the unusual electronic density distribution in DATP ligands as compared with other aza-aromatic ligands. The conditional stability constants of the 1:3 lanthanide(III) complexes with DiPTP have been determined at pH 2.8 and are found to increase almost regularly from La (log β3app = 11.7 ± 0.1) to Lu (log β3app = 16.7 ± 0.8). Moreover, the kinetic stability of the gas-phase 1:3 complexes obtained by electrospray has been investigated by energy-resolved collision-induced dissociation and provides useful information on the bonding and structure.

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